Lubricating oils



Patented Mar. 28, 1950 2,501,992 LUBRICATING OILS James 0. Clayton, Berkeley, Calif., and William H. Alden-son, Baln-ein Island, Arabia, assignora to California Research Corporation, San Francisco, Caliil, a corporation of Delaware No Drawing. Application October 28, 1946.

Serial No. 706,084

8 Claims. (Cl. 252-42.?)

- i This invention relates to hydrocarbon lubricating oils and the like containing a new and useful combination of additive materials. More new and useful combination of additive materials to be incorporated in hydrocarbon lubricating oil and the like to accomplish a higher level of improvement than provided by additive materials and combinations thereof heretofore in use.

It is a further object o! the invention to produce hydrocarbon lubricating oil and the like having in higher degree than heretofore, the following characteristics: high detergency, that is, the property of maintaining pistons, piston rings and piston ring slots in internal combustion engines in a clean condition; resistanc to oxidation; and a low degree of corrosion of alloy bearing s, such as, cadmium-silver and copper-lead bearings.

These and other objects of the invention will be apparent from the following description and the appended claims.

In accordance with the invention, there is incorporated in an oil of lubricating viscosity a small amount each .01 a salt of a phenol containing an ether substituent on the aromatic nucleus and an aliphatic monoor diselenide.

- The composition of the invention, therefore, comprises three ingredients: a base oil, a salt of a phenol, and a selenium compound.

The base oil is preferably a mineral lubricating oiLsuch as a naphthenic, parafiinic or mixed Rr-O-A-O-M in which A is an aromatic nucleus, M is a saltforming atom or radical, and R is an ether-forming group attached to oxygen through carbon.

Preferably, the phenate is a polyvalent metal salt of a mono-ether of a dihydroxy benzene or a homologue of a dihydroxy benzene, and an aliphatic alcohol containing to 30 carbon atoms; most advantageously the phenate is an alkaline earth metal salt of a mono-ether oi resorcinol or a homologue of resorcinol, in which the etherii'ying group is a C10 to Can aliphatic radical.

Examples of suitable salts of phenols are as follows: lithium, sodium, potassium, calcium, strontium, barium, zinc and aluminum salts of ortho, metaand para-pentoxy octoxy, decoxy, cetoxy, octadecoxy, eicosoxy, parafiinoxy and amylcyclohexoxy phenates. These particular examples have the generic formula where R is an amyl, octyl, decyl, cetyl, octadecyl, eicosyl, paraflin or amylcyclohexyl radical (the paramn" radical being derived from paramn wax by chlorination and condensation); M is lithium, sodium, potassium, calcium, strontium, barium, zinc or aluminum; the group 0R is in the ortho, meta or para position with respect to the metaloxy group; and n is the valence of M. Basic and mixed salts may be used in place of normal salts, but the normal salts are preferred.

The selenium compounds of the compositions of the invention have the structure wherein R1 and R2 are aliphatic radicals and m is 1 or 2. Thus, R1 and R: may be alkyl, cycloaliphatic or aralkyl radicals. Preferably R1 and R: are alkyl or aralkyl radicals each containing not less than 7 carbon atoms. Examples of suitable aliphatic selenium compounds are: dibutyl mono-selenide, di-amyl mono-selenide, di-octyl mono-selenide, di-octyl diselenide, octyl dodecyl mono-selenide, di-octadecyl mono-selenide, dioctadecyl diselenide, di-parafiin mono-selenide, di-paraflin diselenide, di-amyloyclohexyl monoselenide, di-amylcyclohexyl diselenide and dibenzyl mono-selenide.

By the term aliphatic radical as used herein, without qualification, is meant radicals attached to selenium (in the case of the selenides) or to oxygen (in the case of the phenates) by a nonbenzenoid carbon atom, and it includes, for example, alkyl, alkylene, cycloalkyl and aralkyl radicals. By selenide as used herein, without qualifications as a monoor diselenide, it is intended to include both the mono-selenides (R1-Se-R2) and diselenides (R1-Sez-R2).

To produce the finished oil of the invention aqueous alcohol. The resorcinol monocetyl 'etherwas recovered from the thinner solution l to produce a concentrate.

. and Condit, United States Patent No. 2,398,414,

issued April 16, 1946. A suitable mode of preparing the phenates of the invention is illustrated by the preparation of barium meta cetyloxy phenate, as follows:

necessary to use a pure aliphatic chloride such as cetyl chloride, but crude mixtures such as chlorinated kerosene and chlorinated parafin wax having an average molecular weight of 175 to 455, and preferably containing about one gram atom of chlorine per average gram molecular weight of mixture, may be used to alkylate the polyhydric phenol.

A further improvement in the preparation of the phenate additive oi the invention is the employment of an excess of the polyhydric phenol. Such excess decreases the yield of di-ether and increases the yield of the desired mono-ether.

Oils of the invention were submitted to test as crankcase lubricants of gasoline engines with Equimolar proportions of resorcinol and cetyl results as shownintha table:

' Table Piston Discolora tion Number Base Oil Compounding so Hrs. Hrs.

LAUSON ENGINE TESTS (l) SAE 30 blend of parailinic and 16 mMJkg Ba m-cetoxy phenate 30 naphthenic oils. (2) do 16 mMJkg. Ba m-cetoxy phenate-{4% dilauryl 25 46 monoselenide. (3) Pennsylvania base oil Same as (2) 20 60 WISCONSIN ENGINE TESTS (4) SAE 50 blend of paraflinic and Nil 620 naihthenic oils. (6) o Sameas (2) 105 E5 (6) do 16 mMJkg. Ba m-cetoxy phenatc+l.54% di- 20 195 paraifm monoselenide. (7) do l6 mM. kg. Ba m-cetoxy phenate+0.625% di- 155 245 benzyl monoselenide. (8) do Nil 580 (9) Sameas(2) 110 (10) ..do l6 mMJkg. Ba m-cetoxy phenatc+0.8% dioctadecyl diselenide.

chloride were dissolved in Cellosolve (trade-name of a product of Carbide and Carbon Chemicals Corp., being the mono-ethyl ether of ethylene glycol) and the solution was heated to reflux. To the refluxing mixture was slowly added solid potassium hydroxide and the refluxing was continued until all of the cetyl chloride had reacted. f'l'he Cellosolve' wasthenremoved by distillation and the reaction mixture was washed out of the flask witha petroleum thinner. Unreact'ed resorcinol and potassium chloride were washed out of the solution, first with water and then with as the potassium salt by washing with potassium hydroxide in 50% aqueous alcohol. The alkaline. alcoholic solution was acidified and the liberated resorcinol monocetyl ether was extracted with petroleum ether and freed of petroleum ether by heating to 250 F. The normal barium salt was prepared by reacting the resorcinol monocetyl ether with barium oxide and the final product was recovered by extraction with lubricating oil The starting material for preparing the phenate additive need not be a pure polyhydric phenol, such as resorcinol, but may be a crude mixture of polyhydroxy benzen'es or homologues of the same. In general, however, meta dihydroxy ben- 1 zene and homologues of the'same are preferred The amount of barium m-cetoxy phenate is stated' in the table as 16 mM./kg., meaning l6 millimols of barium per kilogram of oil. That is, each oil containing the barium salt contained an amount equivalentto 16 millimols of barium per kilogram of oil. 4

. Piston discoloration numbers as given in the table were determined by disassembling the test "piston is rated as having a piston discoloration number (P.'D. No.) of zero, a completely fouled piston, as having a P. D. No. of 800. Further refinements used in, arriving at P. D. Nos.'need not be given as the same method of rating was usedinallcases. r

The test engines were a Lauson single cylinder gasoline engine (oils Nos. (1) to (3)) operated Y at 460 F. jacket temperature and 220 F. oil sump temperature; a Wisconsin single cylinder gasoline engine (oils Nos. (4) to (7)) operated at 600 F. cylinder, 325 F. oil sump temperature; and a similar Wisconsin engine (oils Nos. (8) to (10)) operated at 600 F. cylinder, 220 F. oil sump temperatures.

The phenate and selenium additives of the invention may be used as the only compounding agents or they may be used in conjunction with other additives such as sulfonates (e. g., Ca mahogany sulfonate), phosphates (e. g., Ca cetyl phosphate) and thiophosphates (e. g., calcium and zinc di-cetylphenyl dithiophosphate and zinc di-methylcyclohexyl dithiophosphate) these additives being used in finished oils and in conengines after 30 hours and again after 60 hours and inspecting the piston. .A completely clean s centrates in proportions similar to those given above with regard to the phenates and selenium compounds of the invention.

We claim: 1. A composition of matter consisting essentially 01' a major proportion of a' hydrocarbon oil of lubricating viscosity and about 0.1 to 2% by weight of each based on finished oil of a phenate having the structure ROA-O-M, in which A is an aromatic nucleus, M represents an alkaline earth metal, R is a hydrocarbon radical of 5-30 carbon atoms attached to the oxygen atom through a non-benzenoid carbon atom and the R-O group is in meta position'in relation to the -M group, and a selenium compound having the formula Rl-(Se)1n-R2, wherein R1 and R2 are hydrocarbon radicals or at least 7 carbon atoms and attached to selenium by a non-benunoid carbon atom, and m is 1 or 2.

2. The composition of claim 1 wherein the selenium compound is a dialkyl selenidecontaining not less than 8 carbon atoms in each alkyl group.

3. A mineral lubricating oil containing about 0.1 try 2% by weight each based on finished oil of an alkaline earth metal salt of 9, meta dihydric phenol having an alkyl radical of to 30 carbon wherein R is a hydrocarbon radical or 5-30 carbon atoms and is attached through a non-benzenoid carbon atom to the oxygen atom in meta poaltloninreiationtothemetaloaysroumlfla an alkaline earth metal, and n is the valence of M and a dialkyl selenidecontaining not less than 8 carbon atoms in each alkyl radical.

6. The oil of claim 5, wherein said dihydric phenol is resorcinol.

7. A composition of matter consisting essentially of a major proportion of a hydrocarbon oil of lubricating viscosity and about 0.1 to 2% by weight of each based on finished oil of an alkaline earth metal phenate salt having a hydrocarbon ether ring substituent directly attached through the ether oxygen atom to the aromatic nucleus in the meta position in relation to the metaloxy group, said ether substituent containing 5-30 carbon atoms, and a selenium compound having the formula Ri(Se)mRz, wherein R1 and R2 are hydrocarbon radicals of at least 7 carbon atoms and attached to selenium by a non-benzanoid carbon atom, and m is l or-2. I

8. A lubricantconsisting essentially of a major proportionj-or a hydrocarbon oil of lubricating viscosity in about 0.1 to 2% by weight of each based on finished oil of metal salt of a meta dihydric phenol having substituted for the hydro- "through a non-benzenoid carbon atom, and a gen of one of the hydroxy radicals of the parent dihydric phenol, a hydrocarbon radical of 5-30 carbon atoms directly attached to the oxygen selenium compound having the formula R1--(Se)'|-R:

wherein R1 and R; are hydrocarbon radicals of at least 7 carbon atoms and attached to selenium by a non-benzenoid carbon atom, and m is 1 or 2.

JAMES O. CLAYTON. WILLIAM H. ALDERSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,197,833 Reifl -1 Apr. 23,1940

' 2,344,988 Kavanagh Mar. 28, 1944 2,398,418 Denison Apr. 16, 1948 2,402,448 Y Richards June 18, 1948 

1. A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF A MAJOR PROPORTION OF A HYDROCARBON OIL OF LUBRICATING VISCOSITY AND ABOUT 0.1 TO 2% BY WEIGHT OF EACH BASED ON FINISHED OIL OF A PHENATE HAVING THE STRUCTURE R-O-A-O-M, IN WHICH A IS AN AROMATIC NUCLEUS, M REPRESENTS AN ALKALINE EARTH METAL, R IS A HYDROCARBON RADICAL OF 5-30 CARBON ATOMS ATTACHED TO THE OXYGEN ATOM THROUGH A NON-BENZENOID CARBON ATOM AND THE R-O GROUP IS IN META POSITION IN RELATION TO THE O-M GROUP, AND SELENIUM COMPOUND HAVING THE FORMULA R1-(SE)M-R2, WHEREIN R1 AND R2 ARE HYDROCARBON RADICALS OF AT LEAST 7 CARBON ATOMS AND ATTACHED TO SELENIUM BY A NON-BENZENOID CARBON ATOM, AND M IS 1 OR
 2. 